WO2002098888A1 - Procede de preparation de catalyseurs metalliques a base de carbenes, pour l'hydrosilylation de composes insatures et catalyseurs de ce type - Google Patents

Procede de preparation de catalyseurs metalliques a base de carbenes, pour l'hydrosilylation de composes insatures et catalyseurs de ce type Download PDF

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WO2002098888A1
WO2002098888A1 PCT/FR2002/001896 FR0201896W WO02098888A1 WO 2002098888 A1 WO2002098888 A1 WO 2002098888A1 FR 0201896 W FR0201896 W FR 0201896W WO 02098888 A1 WO02098888 A1 WO 02098888A1
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alkyl
optionally substituted
formula
group
aryl
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PCT/FR2002/001896
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English (en)
French (fr)
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Olivier Buisine
Istvan Marko
Sébastien STERIN
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Rhodia Chimie
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Priority to US10/479,808 priority Critical patent/US7019145B2/en
Priority to DE60210082T priority patent/DE60210082T2/de
Priority to EP02743347A priority patent/EP1392708B1/de
Priority to BRPI0210981A priority patent/BRPI0210981B8/pt
Priority to KR1020037015971A priority patent/KR100595338B1/ko
Publication of WO2002098888A1 publication Critical patent/WO2002098888A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions

Definitions

  • the invention relates to the preparation of catalysts for hydrosilylation reactions and in particular for hydrosilylation of ethylenically and / or acetylenically unsaturated compounds (for example olefins or acetylenic derivatives), in particular but not limited to those involving polyorganosiloxanes (POS) carrying units Si-H and POS carrying S - units (ethylenic or acetylenic unsaturation).
  • POS polyorganosiloxanes
  • the hydrosilylation catalysts are platinum catalysts (US 2,823,218, US 2,970,150).
  • the Karstedt solution which consists of platinum complexes with oxidation state 0.
  • the ideal general formula for the Karstedt complex is Pt 2 (tetramethyldivinylsiloxane ) 3 :
  • a reaction medium comprising a carbene precursor is used: for example 1, 3-dimethylimidazolinium iodide, a solvent system comprising THF and ammonia and a base: NaH.
  • a solution of carbene in THF is obtained.
  • this carbene solution is mixed with a Karstedt platinum complex solution.
  • various stages of filtration, purification, concentration, washing, precipitation, a solid Pt / carbene complex is obtained.
  • US Patent 5,728,839 also discloses the preparation in two stages of metal / carbene complexes, from imidazolium, benzimidazolium, triazolium, tetrazolium or pyrazolium (for example iodide) salts.
  • Carbene is first obtained by bringing together the imidazolium, benzimidazolium, triazolium, tetrazolium or pyrazolium salt with an deprotonating base NaH in solution in THF.
  • the metal complex (Rhodium) is obtained by exchange between carbene and a metal / cycloolefin complex (for example a di ( ⁇ -chloro) -bis- ( ⁇ 4 -1,5-cyclooctadiene) - dirhodium).
  • a metal / cycloolefin complex for example a di ( ⁇ -chloro) -bis- ( ⁇ 4 -1,5-cyclooctadiene) - dirhodium.
  • Another essential objective of the invention is to provide a process for the preparation of metal complexes of formula I, improved with respect to that described in the unpublished prior patent application FR 99 15432 in terms of methodological simplification, increase in yield and cost reduction.
  • Another essential objective of the invention is to provide an improved process for the preparation of metal complexes of formula I used as hydrosilylation catalysts, the latter having to be stable in the reaction medium, so as to: o produce a selective catalytic activity of high qualitative and quantitative level, o and to limit training:
  • Another essential objective of the invention is to provide a process for hydrosilylation and in particular for hydrosilylation of ethylenically and / or acetylenically unsaturated compounds, in the presence of a catalyst comprising the metal complex obtained by the abovementioned process.
  • M represents a metal chosen from the metals of group 8 of the periodic table as published in Handbook of Chemistry and Physics, 65 th edition, 1984-
  • X represents O, NR a or CR f R g ;
  • Yi and Y 2 independently of one another represent CRbR c or SiRdR e ;
  • Ri, R 2 , 3, 4, R5, ⁇ , Ra, b and R c, identical or different, are chosen from a hydrogen atom; an alkyl group; acyl; aryl optionally substituted with alkyl; cycloalkyl optionally substituted with alkyl; and arylalkyl in which the aryl part is optionally substituted by alkyl;
  • R d and R e are independently chosen from alkyl; aryl optionally substituted with alkyl; cycloalkyl optionally substituted with alkyl; and arylalkyl in which the aryl part is optionally substituted by alkyl; or else when Y 1 and Y 2 independently represent SiRdRe, two Rd groups linked to two distinct silicon atoms together form a chain of formula:
  • n is an integer from 1 to 3;
  • X is as defined above;
  • R and R ' identical or different, take any of the meanings given above for R e , it being understood that, when n is 2 or 3, a single silicon atom of the said chain can be substituted by one or two groups alkenyl or alkynyl; or else when Yi and Y 2 independently represent SiRdRe, two groups R d linked to distinct silicon atoms together form a saturated hydrocarbon chain, the two groups Rd together with said silicon atoms and X forming a 6 to 10-membered ring; or when Yi and Y 2 independently represent CRbR c , two Rb groups linked to distinct carbon atoms together form a saturated hydrocarbon chain, the two Rb groups together with the carbon atoms which carry them and X form a 6 to 6 ring.
  • R f and R g independently of one another represent a hydrogen atom; an alkyl group; acyl; aryl optionally substituted with alkyl; cycloalkyl optionally substituted with alkyl; arylalkyl in which the aryl part is optionally substituted by alkyl; a halogen atom; an alkenyl group; an alkynyl group; or a SiG ⁇ G 2 G3 group or G 2 and G 3 are independently of each other alkyl; aikoxy; aryl optionally substituted with alkyl or aikoxy; or arylalkyl in which the aryl part is optionally substituted by alkyl or aikoxy; L represents a carbene of formula (II):
  • - A and B independently represent C or N, it being understood that when A represents N, then T represents nothing and when B represents N, then T 3 represents nothing; - T 3 and T 4 independently represent a hydrogen atom; an alkyl group; cycloalkyl optionally substituted by alkyl or aikoxy; aryl optionally substituted with alkyl or aikoxy; alkenyl; alkynyl; or arylalkyl in which the aryl part is optionally substituted by alkyl or aikoxy; or
  • T 3 and T 4 can form together and with A and B when these each represent a carbon atom, an aryl;
  • T 1 and T 2 independently represent an alkyl group; an alkyl group optionally substituted by alkyl; a perfluorinated alkyl group or optionally substituted by a perfluoroalkyl group; cycloalkyl optionally substituted by alkyl or aikoxy; aryl optionally substituted with alkyl or aikoxy; alkenyl; alkynyl; or arylalkyl in which the aryl part is optionally substituted by alkyl or aikoxy; or
  • T1 and T 2 independently represent a monovalent radical of formula (V) below:
  • V 1 is a divalent hydrocarbon radical, preferably a linear or branched C 1 -C 1 alkylene, optionally substituted
  • V 2 is a monovalent radical chosen from the group of the following substituents:
  • T 1 and T 2 independently represent a monovalent radical of formula (W) below:
  • W ⁇ is a divalent hydrocarbon radical, preferably a linear or branched C 1 -C 1 0 alkylene, optionally substituted,
  • R ⁇ alkyl, H;
  • R ⁇ H, alkyl; alkenyl, alkynyl
  • R ⁇ alkyl; alkenyl, alkynyl; or even the substituents Ti, T 2 , T 3 and T 4 can form two by two, when they are located on two adjacent vertices in formula II, a saturated or unsaturated hydrocarbon chain.
  • Z 1 independently represents an anion derived from a Br ⁇ nsted acid (protic acid) preferably chosen from the group comprising:
  • One of the essential characteristics of the process according to the invention is therefore to provide for the formation of the metal / carbene complex in a single step.
  • the metal complexes concerned by the process according to the invention are defined below.
  • the group 8 metals represented by M are, for example, palladium, platinum or nickel with an oxidation state of 0. In practice, M represents platinum in an oxidation state of 0.
  • alkyl is meant a saturated, linear or branched hydrocarbon chain, optionally substituted (eg by one or more alkyls), preferably from 1 to 10 carbon atoms, for example from 1 to 8 carbon atoms, better still from 1 to 7 carbon atoms.
  • alkyl groups include methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, n-pentyl, isoamyl and 1, 1-dimethylpropyl.
  • the alkyl part of the alkoxy radical is as defined above.
  • the perfluoroalkyl radical or optionally substituted with a perfluoroalkyl group preferably has the formula: in which p represents 0, 1, 2, 3 or 4; q is an integer from 1 to 10; and CqF 2 q + ⁇ is linear or branched.
  • Preferred examples of this radical are: - (CH 2 ) 2— (CF 2 ) 5 - CF 3 and— (CF 2 ) ⁇ — CF 3 .
  • aryl designates an aromatic hydrocarbon group, having from 6 to 18 carbon atoms, monocyclic or polycyclic and preferably monocyclic or bicyclic.
  • polycyclic aromatic radical is meant a radical having two or more aromatic rings, condensed (orthocondensed or ortho and pericondensed) to each other, that is to say having, two by two, at least two carbons in common.
  • aromatic hydrocarbon group is optionally substituted for example by one or more C1-C 3, one or more halogenated hydrocarbon radicals (eg CF 3), one or more alkoxy (eg CH 3 O) or one or several hydrocarbon radicals comprising one or more ketone units (eg CH 3 CO-).
  • halogenated hydrocarbon radicals eg CF 3
  • alkoxy eg CH 3 O
  • hydrocarbon radicals comprising one or more ketone units
  • arylalkyl designates an alkyl group as defined above, substituted by one or more aryl groups on its hydrocarbon chain, the aryl group being as defined above. Examples are benzyl and triphenylmethyl.
  • acyl is meant a group R 0 -CO- where R 0 represents alkyl as defined above; or an Ar-CO- group where Ar represents an aryl group as defined above, or else arylalkyl in which aryl and alkyl are as defined above and in which the aryl part is optionally substituted eg by alkyl.
  • cycloalkyl is meant a saturated hydrocarbon radical mono- or polycyclic, preferably mono- or bicyclic, preferably having from 3 to 10 carbon atoms, better still from 3 to 8.
  • saturated hydrocarbon radical polycyclic means a radical having two or more cyclic nuclei attached to each other by ⁇ or / bonds and condensed two by two.
  • Examples of polycyclic cycloalkyl groups are adamantane and norbornane.
  • Examples of monocyclic cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • alkenyl is meant an unsaturated, linear or branched hydrocarbon chain, substituted or not, having at least one olefinic double bond, and more preferably a single double bond.
  • the alkenyl group has from 2 to 8 carbon atoms, better still from 2 to 6.
  • This hydrocarbon chain optionally comprises at least one heteroatom such as 0, N, S.
  • alkenyl groups are the allyl and homoallyl groups.
  • alkynyl is meant according to the invention, an unsaturated hydrocarbon chain, linear or branched, substituted or not, having at least one acetylenic triple bond, and more preferably a single triple bond.
  • the alkynyl group has from 2 to 8 carbon atoms, better still from 2 to 6 carbon atoms.
  • acetylenyl group as well as the propargyl group.
  • This hydrocarbon chain optionally comprises at least one heteroatom such as 0, N, S.
  • the expression "represents nothing” means that the substituents -T 3 , respectively -T 4 , are nonexistent.
  • the nitrogen atom is trivalent, so that when A or B represents N, the nitrogen atom cannot have an additional substituent.
  • the carbenes of formula (II) can have at least two condensed rings, that is to say that at least two substituents among Ti, T 2 , T 3 and T 4 , located on two adjacent vertices, together form a hydrocarbon chain saturated or unsaturated, preferably having 3 to 6 carbon atoms.
  • saturated or unsaturated hydrocarbon chain is meant a linear or branched hydrocarbon chain which may or may not have one or more unsaturations of the olefinic double bond or acetylene triple bond type.
  • carbenes (II) have two condensed nuclei, they therefore correspond to one of the following formulas, in which (alk) represents a saturated or unsaturated hydrocarbon chain:
  • carbenes II can have more than two condensed nuclei.
  • the complexes which are preferably prepared by the process according to the invention, are those in which Yi and Y 2 represent either both CR b R c , or both SiRdRe, so that said complexes have either for formula (1.1), or for formula (1.2):
  • R b 1 and R c 1 are the substituents R b and R G of Yi in formula (1.1);
  • R b 2 and Rc 2 are the substituents R b and R c of Y 2 in formula (1.2);
  • R d 1 and R e 1 are the substituents R d and R e of Yi in formula (1.1);
  • R d 2 and R e 2 are the substituents R and R e of Y 2 in formula (1.2).
  • Rb 1 can be the same or different from R 2 ;
  • R c 1 may be the same or different from R c 2 ;
  • R d 1 may be the same or different from R d 2 ;
  • R e 1 can be the same or different from R e 2 .
  • R d 1 and R 2 together form:
  • R and R ' identical or different, take any of the meanings given above for R e , it being understood that, when n is 2 or 3, a single silicon atom of the said chain may be substituted by one or two alkenyl or alkynyl groups;
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R e
  • R e R preferably represents alkyl, for example methyl.
  • R 5 R 2 ;
  • R 3 R 4 -
  • R d and R d 2 form the chain (b)
  • R e 1 is identical to R e 2 .
  • T represents alkyl
  • i is an integer between 0 and 5
  • T being located on one or more of the vertices 1, 2, 3, 4 and 5 of the above formula.
  • the two groups R b linked to distinct carbon atoms can together form a saturated hydrocarbon chain (c), so that the two groups R b together with the carbons carrying them and X form a 6 to 10-membered ring.
  • the ring formed is an 8-membered ring, in which case the metal complex corresponds to the formula:
  • T represents alkyl
  • i is an integer between 0 and 5, T being located on one or more of the vertices 1, 2, 3, 4 and 5 of the above formula.
  • R e 1 R ⁇ 2 -
  • R f and / or R g represents SiG ⁇ G 2 G 3
  • Subgroups of the metal complexes of the invention consist of the complexes for which:
  • Y1 and Y 2 independently represent SiR Re; or
  • X represents O and Yi and Y 2 independently represent SiRdR e in the metal complex of formula (I).
  • the expression "independently represent” means that the designated substituents are either identical or different.
  • Ri, R2, R5 and R 6 are hydrogen atoms.
  • R 3 and R 4 are in particular a hydrogen atom; an alkyl group; aryl optionally substituted with alkyl; and cycloalkyl optionally substituted with alkyl.
  • R 3 and R 4 which are identical, represent a hydrogen atom; (C 3 -C 8 ) cycloalkyl or (C ⁇ -C 8 ) alkyl.
  • a preferred group of complexes according to the invention consists of the complexes of formula (I) in which L represents a carbene of formula (II).
  • L represents a carbene of formula (II).
  • a and B in formula (II) both represent a carbon atom.
  • - cycloalkyl in particular cyclopentyl, cyclohexyl or adamantyl
  • T 3 and T 4 both correspond to hydrogen or together form an aryl, and better still a phenyl.
  • a particularly preferred group of metal complexes of formula (I) consists of the complexes of formula:
  • T 1 and T 2 are identical and are as defined above; T 3 and T 4 are as defined above; R d and R e are as defined above.
  • the present invention relates, as new products, to complexes of formula (I) in which the carbene of formula (II) is such that:
  • T3 and T 4 can form together and with A and B when these each represent a carbon atom, an aryl as defined above, preferably a phenyl;
  • T 1 and T 2 independently represent a monovalent radical of formula (V) below:
  • V 1 is a divalent hydrocarbon radical, preferably a linear or branched C 1 -C 10 alkylene, optionally substituted,
  • V 2 is a monovalent radical chosen from the group of the following substituents: 4 alkoxy, -OR v with R v corresponding to hydrogen, alkyl, aryl amino, preferably N (R V ) 2 with R v corresponding to hydrogen, alkyl, aryl
  • T 1 and T 2 independently represent a monovalent radical of formula (W) below: in which :
  • W ⁇ is a divalent hydrocarbon radical, preferably a linear or branched C1-C10 alkylene, optionally substituted, • ⁇ represents:
  • R ⁇ C CR ⁇ - with R ⁇ corresponding to H or alkyl or
  • R alkyl; alkenyl, alkynyl
  • R ⁇ H, alkyl; alkenyl, alkynyl;
  • ⁇ _ alkyl; alkenyl, alkynyl;
  • CH 2 -C C— Si (CH 3 ) 3 or alternatively to one of the following methyl, isopropyl, tert-butyl, n-pentyl, neo-pentyl, cyclopentyl, cyclohexyl, adamantyl, allyl, methallyl, propargyl or homopropargyl units.
  • the anion Zi " is the anion derived from an organic or mineral Brônsted acid (protic acid).
  • the anion Zi " is derived from an acid having a pKa lower than 6
  • Zi " derives from an acid with a pKa of less than 4, better still less than 2.
  • the pKa in question here are the pKa of the acids as measured in water.
  • acids are the carboxylic acids of formula: G 0 -COOH, in which G 0 represents alkyl, and for example (C- ⁇ -C 22 ) alkyl; or else aryl, and for example (C 6 -C ⁇ 8 ) aryl optionally substituted by one or more alkyls, preferably one or more (CrC ⁇ Jalkyle; sulfonic acids of formula: G 0 -S0 3 H in which G 0 is as defined above; and the phosphonic acids of formula: G 0 -P0 3 H in which G 0 is as defined above; other acids are HF, HCI, HBr, Hl, H 2 SO ) H 3 PO, HCI0 and HBF 4 .
  • carboxylic acids are acetic acid, benzoic acid, and stearic acid.
  • sulfonic acid benzene sulfonic acid will be mentioned and as preferred phosphonic acid, phenylphosphonic acid will be mentioned.
  • the Zi " anions derived from HCI, Hl and HBF 4 acids are more particularly preferred.
  • particularly preferred Zi " anions according to the invention are the halide anions and the tetrafluoroborate.
  • Suitable precursor complexes (IV) are in particular the complexes of formula:
  • solvent (V) it is chosen so that the solubility of the salt
  • the solvent (V) is selected from polar aprotic solvents whose boiling point at 1 atm is less than 150 ° C, preferably at 120 ° C, preferably from the group comprising:
  • the solvent (V) must not only provide a reaction environment conducive to the formation of carbene / metal complexes, but also be neutral and easily removable.
  • the base (VI) it is chosen according to its capacity to deprotonate the salt (III) at least partially dissolved in the solvent (V).
  • the concentration of the base (VI) in the reaction medium is defined as follows [in moles / 1 of solvent (V)]:
  • the base (VI) is not in an excess such that this causes a parasitic reaction with the constituents of the reaction medium other than the salt III to be deprotonated.
  • the salt (III) and the base (VI) are used in quantities such that the ratio Rvi / m of normality VI / III is defined as follows:
  • T 3 and T 4 are as defined above with HCHO and two amines of formulas T- ⁇ -NH 2 and T 2 -NH 2 in the presence of an appropriate acid.
  • the nature of the anion Z 1 in the salts of formula III depends on the acid used in this step.
  • the acids which can be used are, for example, those listed above and from which Zi is derived.
  • Other methods of preparing the salts of formula (III) are proposed in Chem. Eur. J. 1996, 2, n ° 12, pages 1627-1636 and Angew. Chem. Int. Ed. Engl. 1997, 36, 2162-2187.
  • the process which it relates essentially consists in: a) dissolving the salt (III) and the compound (IV) in the solvent (V), b) incorporating into several times the base (VI) in the solution of (III) and (IV) in (V), c) maintain the reaction medium thus constituted under stirring, until formation of the compound (I), d) recover the compound ( I) formed, preferably by evaporation, e) optionally purification, f) optionally drying.
  • steps b) and c) are carried out at a temperature between -78 ° C and 50 ° C, preferably at 0 ° C and at atmospheric pressure.
  • the reaction time (steps a), b), c)) can vary for example from 2 hours to 48 hours. It takes an average of 5 hours. This duration decreases with the solubility of salt III in the medium. If the precursor salt is soluble in solvent V, the duration of the reaction may be less than 1 hour.
  • T 2 are identical and represent (C ⁇ -C 8 ) alkyl or (C 3 -C 8 ) cycloalkyl;
  • T are identical and represent hydrogen or together represent a phenyl
  • - Z ⁇ is a halogen, preferably Cl, I, or BF 4 ;
  • Rd, Re are identical and represent CH 3 ; • a solvent (V) comprising THF,
  • VT tetf-butoxide
  • the invention relates to a catalytic composition
  • a catalytic composition comprising, as active material, one or more metal complexes prepared by implementing the method according to the invention.
  • the catalysts thus prepared can be used in hydrosilylation reactions. They allow a homogeneous catalysis of the reaction.
  • the invention therefore also relates to a process for hydrosilylation and in particular for hydrosilylation of ethylenically and / or acetylenically unsaturated compounds, characterized in that it is carried out in the presence of a catalyst comprising the metal complex obtained by the process described above.
  • ethylenically and / or acetylenically unsaturated compounds designates in particular organic compounds of the olefin type or acetylenic derivative, as well as organomineral compounds, such as organosilicics such as for example vinylsilicon and / or acetylsilicon derivatives .
  • hydrosilylation reaction is understood to mean, according to the invention, the reaction of a compound with an ethylenic double bond or with an acetylenic triple bond (unsaturated compound) with a compound having at least one unit o i - H ⁇ a ç 0n to form a C-Si bond.
  • hydrosilylation reaction can be diagrammed as follows, in the case of a compound with an ethylenic double bond:
  • Compounds with an ethylenic double bond can comprise one or more double bonds and from 2 to 40 carbon atoms. These compounds may be aliphatic hydrocarbons with a linear or branched hydrocarbon chain, or else cyclic hydrocarbons, said cyclic or aliphatic hydrocarbons optionally bearing one or more substituents of the (C 6 -C ⁇ 8 ) aryl type optionally substituted by (C ⁇ -C ⁇ ) alkyl . Double bonds are usually terminal.
  • olefins examples include 2-methylbutene-1, 1-hexene, 1-heptene, 1-octene, 3-ethylhexene-1, 1-decene, 4,4-dimethylnonene-1, vinylcyclohexene, styrene and 2-vinylnaphthalene, PolyOrganoSiloxanes (POS) comprising at least one Si-vinyl per molecule.
  • POS PolyOrganoSiloxanes
  • Compounds with an acetylene triple bond can comprise one or more triple bonds and from 2 to 40 carbon atoms. These compounds are generally aliphatic hydrocarbons with a linear or branched hydrocarbon chain, optionally substituted by (C 3 -C- ⁇ o) cycloalkyle (which cycloalkyle can optionally carry one or more (CrC 6 ) alkyl) or / and by (C 6 - C ⁇ o) aryl (which aryl may optionally carry one or more (C ⁇ -C ⁇ ) alkyl).
  • the compounds with an acetylene triple bond have a single triple bond.
  • the triple bonds are generally terminal. Examples are: 2-propynyl, 1 -propynyl and 2-penten-4-ynyle.
  • hydrosilylation of compounds comprising both one or more ethylenic double bonds and one or more triple acetylenic bonds can also be envisaged in the context of the invention.
  • the hydrosilylation reaction can be carried out in a solvent or in the absence of a solvent.
  • one of the reagents can act as a solvent: for example the compound with an ethylenic double bond or with an acetylene triple bond.
  • Suitable solvents are solvents miscible with the compound containing the Si-H unit.
  • the catalyst complex Under the conditions of the hydrosilylation reaction, the catalyst complex must be dissolved in the reaction medium.
  • the compound with Si-H unit can be a silicon hydride of formula (XIII):
  • X is a radical comprising a heteroatom such as O, Si, a halogen atom or the carbon atom of an aliphatic or aromatic group;
  • R is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group or a cycloalkoxy group; a is an integer from 0 to 3.
  • the aliphatic, aromatic, alkyl, aryl, cycloalkyl, alkoxy, aryloxy, cycloalkoxy groups may or may not be substituted.
  • the nature of the substituents is defined so as not to give rise to side reactions during the hydrosilylation reaction.
  • silane HSi (OC 2 H 5 ) 3 and HSi (C 2 H 5 ) 3 .
  • the compound having a Si-H unit can be a polymer of the polyhydrogenosiloxane type.
  • suitable polymers and copolymers are polyhydrogenosilanes comprising a large number of repeating units containing Si-H bonds.
  • the polymers which can be used have recurring units of formula: HI.
  • X is a radical comprising a heteroatom such as O, Si or the carbon atom of an aliphatic or aromatic group
  • R 0 is a hydrogen atom or an organic group chosen from alkyl, aryl, cycloalkyl, alkoxy, aryloxy or cycloalkoxy.
  • R 7 to R13 are independently a hydrogen atom or an organic group.
  • R 7 , R 8 , Rg, R10, R11, R12 and R 13 are chosen from a hydrogen atom, an alkyl, aryl, cycloalkyl, alkoxy, aryloxy and cycloalkoxy group; n is an integer at least equal to 1 and preferably at least equal to 10 and, better still, comprised between 10 and 100.
  • Suitable polymers are polymethylhydrogenosiloxanes with -Si (CH 3 ) 3 ends and polydimethylsiloxanes with -Si (CH 3 ) 2 H ends, methylhydrogenodimethylsiloxane copolymers with -Si (CH3) 2 H ends, methylhydrogenomethyloctylsiloxane copolymers, and methylhydroxy polymers
  • the polymers which can be used in the reaction have an average molecular mass of 300 or more and preferably between 300 and 10,000 (g / mol).
  • Examples of silicon hydrides are described in US-A-5359 113.
  • solvents which can be used for hydrosilylation are in particular aliphatic hydrocarbons (such as pentane, hexane, heptane, pentamethylheptane or petroleum distillation fractions); aromatic hydrocarbons (such as benzene, toluene and xylenes: ortho-xylene para-xylene and meta-xylene); halogenated aliphatic or aromatic hydrocarbons (such as tetrachlorethylene); or ethers (such as tetrahydrofuran or dioxane).
  • aliphatic hydrocarbons such as pentane, hexane, heptane, pentamethylheptane or petroleum distillation fractions
  • aromatic hydrocarbons such as benzene, toluene and xylenes: ortho-xylene para-xylene and meta-xylene
  • the hydrosilylation reaction can be carried out at a temperature of between 15 ° C and 300 ° C, for example between 20 and 240 ° C, better still between 70 and 200 ° C, especially between 50 and 140 ° C, very preferably between 50 and 100 ° C.
  • the relative amount of unsaturated compound and compound having an Si-H unit can be controlled so as to ensure the reaction of all unsaturations with Si-H bonds. It is nevertheless preferable to operate in the presence of a molar excess of unsaturation.
  • the molar ratio of unsaturations to Si-H bonds varies between 1: 100 and 10: 1.
  • the hydrosilylation reaction is carried out in the presence of a catalytic amount of one or more complexes prepared according to the invention.
  • catalytic amount means less than a molar equivalent of platinum relative to the amount of unsaturations present in the reaction medium.
  • the unsaturated compound, the catalyst and the solvent are placed, with stirring, in a reactor.
  • the whole is brought to the desired temperature and the compound with Si-H motifs is introduced, with stirring.
  • A, B, Ti, T 2 , T 3 , T, Zi being as defined above;
  • the imidazolium salt is placed in the presence of the platinum complex in THF.
  • a strong base potassium tert-butoxide
  • the reaction mixture makes it possible to form the carbene, which exchanges quickly with one of the olefins complexed with metal to lead to the corresponding platinum-carbene.
  • the yields and selectivity of the reaction are good.
  • this method is advantageous because of its simplicity of implementation.
  • the Karstedt complex solution and the imidazolium salt are dissolved in THF.
  • the potassium tert-butoxide is added over 1 hour at a temperature of 0 ° C. and the whole is maintained for five hours with stirring.
  • the reaction medium is concentrated under vacuum.
  • the residue is taken up in 30 ml of dichloromethane.
  • This organic phase is then washed with 3 times 20 ml of water and then twice 20 ml of a saturated NaHCO 3 solution .
  • the organic phase is recovered and then concentrated under vacuum.
  • the solid residue is then washed with 3 times 2 ml of ethanol. 1.8 g of an analytically pure white solid are thus obtained (yield 71%).
  • the Karstedt complex solution and the imidazolium salt are diluted in 80 ml of THF.
  • the potassium tert-butoxide is added at temperature ambient and the whole is maintained for ten hours with stirring protected from light.
  • the reaction medium is evaporated and the solid obtained is purified by rapid filtration on silica gel (eluent CH 2 CI 2 ). After evaporation of the solvent, the whole is rinsed with two milliliters of hexamethyldisiloxane and then dried under vacuum. 640 mg of an analytically pure white solid are obtained (yield 98%).
  • the Karstedt complex solution and the benzimidazolium salt are placed in the flask and then diluted in 20 ml of THF.
  • the potassium tert-butoxide is added at room temperature and the whole is kept thirty six hours with stirring protected from light.
  • the reaction medium is diluted in dichloromethane and then washed with water.
  • the solvent is evaporated off, and the oil obtained is quickly filtered through silica gel (eluent CH 2 CI 2 ). After evaporation of the solvent, the solid obtained is rinsed with 2 milliliters of hexamethyldisiloxane. 173 mg (yield 66%) of an analytically pure white solid are obtained.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
PCT/FR2002/001896 2001-06-07 2002-06-04 Procede de preparation de catalyseurs metalliques a base de carbenes, pour l'hydrosilylation de composes insatures et catalyseurs de ce type WO2002098888A1 (fr)

Priority Applications (5)

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US10/479,808 US7019145B2 (en) 2001-06-07 2002-06-04 Method for preparing metallic carbene-based catalysts for hydrosilylation of unsaturated compounds and resulting catalysts
DE60210082T DE60210082T2 (de) 2001-06-07 2002-06-04 Verfahren zur herstellung von katalysatoren auf basis metallischer carbene zur hydrosilylierung von ungesättigten verbindungen und die so erhaltenen katalysatoren
EP02743347A EP1392708B1 (de) 2001-06-07 2002-06-04 Verfahren zur herstellung von katalysatoren auf basis metallischer carbene zur hydrosilylierung von ungesättigten verbindungen und die so erhaltenen katalysatoren
BRPI0210981A BRPI0210981B8 (pt) 2001-06-07 2002-06-04 processo de preparação de complexos metálicos e processo de hidrossililação de compostos etilenicamente e/ou acetilenicamente insaturados
KR1020037015971A KR100595338B1 (ko) 2001-06-07 2002-06-04 불포화 화합물의 수소규소화용 금속 카르벤계 촉매의 제조방법 및 이로부터 수득한 촉매

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FR01/07475 2001-06-07
FR0107475A FR2825707B1 (fr) 2001-06-07 2001-06-07 Procede de preparation de catalyseurs metalliques a base de carbenes, pour l'hydrosilylation de composes insatures et catalyseurs de ce type

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8481522B2 (en) 2008-03-03 2013-07-09 Sanofi Platinum-N-heterocyclic carbene derivatives, preparation thereof and therapeutic use thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1506251B1 (de) * 2002-05-23 2008-10-15 Rhodia Chimie Silikonzusammensetzung, die durch hydrosilylierung in gegenwart eines carben-metall-katalysators vernetzt werden kann und katalysator
FR2882757B1 (fr) * 2005-03-04 2007-04-20 Rhodia Chimie Sa Utilisation d'un compose particulier du platine pour ameliorer la resistance des elastomeres silicones contre la degradation sous l'effet des tres hautes temperatures
US8236915B2 (en) * 2009-07-10 2012-08-07 Momentive Performance Materials Inc. Hydrosilylation catalysts
US10000515B2 (en) 2014-08-12 2018-06-19 Kyushu University, National University Corporation Hydrosilylation reaction catalyst
JP6761997B2 (ja) 2014-08-19 2020-09-30 国立大学法人九州大学 ヒドロシリル化鉄触媒
CN105854946B (zh) * 2016-03-03 2018-07-06 中科院广州化学有限公司南雄材料生产基地 一种含铂硅氢加成催化剂及其制备方法
CN105854945B (zh) * 2016-03-03 2018-03-20 中科院广州化学有限公司南雄材料生产基地 一种可稳定储存含铂硅氢加成催化剂及其制备方法
CN105797778B (zh) * 2016-03-31 2018-05-18 中科院广州化学有限公司南雄材料生产基地 具有抗金属离子干扰作用的含铂硅氢加成催化剂及制备与应用
CN105797777B (zh) * 2016-03-31 2018-03-20 中科院广州化学有限公司南雄材料生产基地 一种二氧化硅固载含铂硅氢加成催化剂及制备方法与应用
CN106380488B (zh) * 2016-07-22 2019-03-29 杭州师范大学 一种Si-O-Si链桥连的N-杂环卡宾铂配合物及其制备方法与应用
CN109970980A (zh) * 2017-12-28 2019-07-05 埃肯有机硅（上海）有限公司 单组分加成型聚硅氧烷组合物
RU2752784C1 (ru) * 2020-12-15 2021-08-03 федеральное государственное автономное образовательное учреждение высшего образования "Казанский (Приволжский) федеральный университет" (ФГАОУ ВО КФУ) Способ получения катализатора гидросилилирования на основе комплекса платины с карбеновыми лигандами и катализатор гидросилилирования, полученный данным способом

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2823218A (en) * 1955-12-05 1958-02-11 Dow Corning Process for the production of organo-silicon compounds
US2970150A (en) * 1957-12-17 1961-01-31 Union Carbide Corp Processes for the reaction of silanic hydrogen-bonded siloxanes with unsaturated organic compounds with a platinum catalyst
US3775452A (en) * 1971-04-28 1973-11-27 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US5359113A (en) * 1993-11-08 1994-10-25 Dow Corning Corporation Method for maintaining catalytic activity during a hydrosilylation reaction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2823218A (en) * 1955-12-05 1958-02-11 Dow Corning Process for the production of organo-silicon compounds
US2970150A (en) * 1957-12-17 1961-01-31 Union Carbide Corp Processes for the reaction of silanic hydrogen-bonded siloxanes with unsaturated organic compounds with a platinum catalyst
US3775452A (en) * 1971-04-28 1973-11-27 Gen Electric Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes
US5359113A (en) * 1993-11-08 1994-10-25 Dow Corning Corporation Method for maintaining catalytic activity during a hydrosilylation reaction

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ENDERS, DIETER ET AL: "Diastereoselective synthesis of chiral (triazolinylidene)rhodium complexes containing an axis of chirality", EUR. J. INORG. CHEM., no. 7, 1998, pages 913 - 919, XP002189972 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8481522B2 (en) 2008-03-03 2013-07-09 Sanofi Platinum-N-heterocyclic carbene derivatives, preparation thereof and therapeutic use thereof
US8980875B2 (en) 2008-03-03 2015-03-17 Centre National De La Recherche Scientifique Platinum-N-heterocyclic carbene derivatives, preparation thereof and therapeutic use thereof

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FR2825707A1 (fr) 2002-12-13
BRPI0210981B8 (pt) 2015-10-06
CN1331873C (zh) 2007-08-15
DE60210082T2 (de) 2006-10-19
KR100595338B1 (ko) 2006-06-30
DE60210082D1 (de) 2006-05-11
ES2256491T3 (es) 2006-07-16
EP1392708B1 (de) 2006-03-22
CN1518555A (zh) 2004-08-04
ATE321060T1 (de) 2006-04-15
FR2825707B1 (fr) 2004-11-26
US20040198996A1 (en) 2004-10-07
BR0210981B1 (pt) 2013-07-23
KR20040007659A (ko) 2004-01-24
PL207962B1 (pl) 2011-02-28
EP1392708A1 (de) 2004-03-03
US7019145B2 (en) 2006-03-28
BR0210981A (pt) 2004-12-21

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